CN110627650B - Device for continuously synthesizing benzylamine substances through heterogeneous hydrogenation in microreactor - Google Patents
Device for continuously synthesizing benzylamine substances through heterogeneous hydrogenation in microreactor Download PDFInfo
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
Abstract
The invention belongs to the technical field of chemical reactions, and particularly relates to a device for continuously synthesizing benzylamine substances by heterogeneous hydrogenation in a microreactor, which comprises: an inlet micromixer (1), an inlet micromixer (2), a micro packed bed reactor (3) and an outlet phase-splitting tank (4). The method utilizes the high-efficiency mixing and excellent mass transfer and heat transfer performance of the microreactor, strengthens the interphase mass transfer and heat transfer capacity in the reaction process, can obviously reduce the volume of the reactor, improves the reaction yield, and improves the production efficiency and safety. The method can solve the problems of low production efficiency, poor product purity, high device danger and the like in the hydrogenation kettle process, can realize continuous automatic operation of the process, and has the advantages of high yield, good safety and the like.
Description
Technical Field
The invention belongs to the technical field of chemical reactions, and particularly relates to a method for continuously synthesizing benzylamine substances through heterogeneous hydrogenation in a microreactor.
Background
Benzylamine substances, such as monobenzylamine, dibenzylamine and p-tert-butylbenzylamine, are important organic synthesis intermediates and are widely used in the industries of medicines, pesticides, dyes and the like. Common methods for producing such materials are benzyl chloride, benzonitrile hydrogenation and benzaldehyde reductive amination. The benzyl chloride method has simple and mature process, but the process has low yield and poor product quality, generates a large amount of salt-containing wastewater, does not meet the requirement of clean production, and is gradually eliminated. The benzonitrile process has high product quality, simple process, but high raw material cost. Therefore, the benzaldehyde reductive amination method is the most promising synthesis process in the comprehensive view, and has the advantages of low cost, clean process and high product quality.
At present, the industrial benzaldehyde reductive amination method generally adopts a high-pressure hydrogenation kettle to complete the reaction, and has the advantages of simple process and flexible operation. However, the method has the disadvantages of complicated operation and frequent loading and unloading of the catalyst; the reaction efficiency is low, the catalyst consumption is large and the catalyst is easy to lose; the reactor has large volume and poor safety; poor control precision of process conditions, low product purity and the like. The micro-reactor has the advantages of high mixing efficiency, good mass transfer and heat transfer performance, good safety and the like, is used for an organic synthesis process, can realize the continuity of the process, reduces the volume of the reactor, and improves the yield and the safety of the reaction. Therefore, the method for producing benzylamine substances by efficient heterogeneous hydrogenation based on the microreactor technology can reduce the volume of a reactor, improve the process safety, improve the production capacity and the product purity, and has important economic, safe and environmental protection values.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a method for continuously synthesizing benzyl amine substances by heterogeneous hydrogenation of a microreactor aiming at the characteristics of the synthesis process of the benzyl amine substances. The method utilizes the high-efficiency mixing and excellent mass transfer and heat transfer performance of the microreactor, strengthens the interphase mass transfer and heat transfer capacity in the reaction process, can obviously reduce the volume of the reactor, improves the reaction yield, and improves the production efficiency and the safety.
Means for solving the technical problem
Aiming at the problems, the invention provides a device for continuously synthesizing benzylamine substances by heterogeneous hydrogenation in a microreactor and a using method thereof.
According to one embodiment of the present invention, there is provided an apparatus for the continuous synthesis of benzylamine species by heterogeneous hydrogenation in a microreactor, comprising: the device comprises an inlet micro mixer (1), an inlet micro mixer (2), a micro packed bed reactor (3) and an outlet phase splitting tank (4), wherein the inlet micro mixer (1) is used for mixing a substrate to be hydrogenated with an ammonia source to form a mixed solution; the inlet micro mixer (2) is used for mixing the first mixed liquid with hydrogen to form gas-liquid mixed fluid; the micro packed bed (3) is filled with a solid catalyst for carrying out heterogeneous hydrogenation reduction reaction; the outlet phase separation tank (4) is used for separating the liquid after reaction from gas and liquid.
In one embodiment, the micromixer comprises a membrane dispersion reactor, a micromesh reactor, a T-reactor or other microreactor capable of achieving mixing of the system.
In one embodiment, the solid particulate catalyst is a palladium on carbon catalyst, palladium on alumina, platinum on carbon, ruthenium on carbon catalyst, ruthenium on alumina, nickel on alumina, or raney nickel catalyst.
According to a second aspect of the present invention, there is provided a method for the continuous synthesis of benzylamine species by heterogeneous hydrogenation in a microreactor, comprising the steps of:
(1) preparing a solution of a substrate to be hydrogenated, mixing the substrate to be hydrogenated with an ammonia source in an inlet micro mixer (1), and mixing the formed mixed solution with hydrogen in an inlet micro mixer (2) to form a gas-liquid mixed fluid;
(2) enabling the gas-liquid mixed fluid obtained in the step (1) to flow through a micro packed bed reactor (3) filled with a solid particle catalyst to carry out heterogeneous hydrogenation reduction reaction;
(3) and (3) in an outlet phase-splitting tank (4), carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), returning the separated hydrogen to the micro mixer (2) in the step (1) for recycling, and separating and purifying the separated solution to obtain benzylamine substances.
In one embodiment, the mass concentration of the substrate to be hydrogenated in the organic solvent is 5-40 wt%, and the substrate is selected from benzaldehyde and tert-butyl benzaldehyde.
In one embodiment, the solvent for dissolving the hydrogenation substrate is one or more of methanol, ethanol, propanol and ethyl acetate.
In one embodiment, the ammonia source is ammonia gas or ammonia water, wherein the mass concentration of the ammonia water is 25-40 wt%.
In one embodiment, the molar ratio of the ammonia source to the substrate to be hydrogenated is 0.5-15: 1.
One embodiment is that one or more of tetraethylammonium chloride, tetrabutylammonium hydroxide, benzyltriethylammonium chloride and tetrabutylammonium bromide can be added into a substrate solution to be hydrogenated as a phase transfer catalyst, and the dosage of the phase transfer catalyst is 0.2-0.5 wt% of the concentration of the substrate to be hydrogenated.
In one embodiment, the reaction temperature of the micro packed bed reactor (3) is 30-150 ℃, and the pressure is 0.4-10 MPa; the residence time of the gas-liquid mixture in the micro packed bed reactor (3) is 0.5-30 min.
The invention has the advantages of
(1) In the process of producing benzylamine substances through heterogeneous hydrogenation, the gas-liquid-solid three-phase contact area in the micro packed bed reactor is large, the mass transfer efficiency is high, and the catalyst consumption and the equipment volume can be reduced;
(2) the gas phase and the liquid phase in the micro packed bed reactor are uniformly distributed, the heat transfer capacity of the micro packed bed is strong, the local excessive hydrogenation is avoided, the generation of byproducts is reduced, and the service life of the catalyst is prolonged;
(3) the reaction time is accurate and controllable, byproducts can be further reduced, and the selectivity is improved;
(4) the reactor has small volume and high safety.
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Drawings
FIG. 1 is a schematic view of an apparatus for continuously synthesizing benzylamine substances by heterogeneous hydrogenation in a microreactor according to the present invention
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto.
Examples
The present invention is described in more detail by way of examples, but the present invention is not limited to the following examples.
Example 1:
according to the method, an experiment is carried out, an ethyl acetate solution of benzaldehyde is prepared, the concentration of the ethyl acetate solution is 5 wt%, the ethyl acetate solution and ammonia gas are mixed in an inlet membrane dispersion micro-mixer 1, the molar ratio of ammonia to benzaldehyde is controlled to be 15:1, then the ethyl acetate solution and hydrogen gas are mixed in an inlet membrane dispersion micro-mixer 2, the formed gas-liquid mixture passes through a micro packed bed reactor filled with a Raney nickel catalyst, the reaction temperature is controlled to be 150 ℃, the pressure is controlled to be 5.0MPa, the residence time is controlled to be 0.5min, gas-liquid phase separation is carried out at the outlet of the micro packed bed, the obtained ethyl acetate solution is analyzed, the conversion rate of the reaction is 100%, and the yield of.
Example 2:
according to the method, an experiment is carried out, a methanol solution of benzaldehyde is prepared, the concentration of the methanol solution is 10 wt%, the methanol solution and ammonia gas are mixed in an inlet micro-sieve-pore micro-mixer 1, the molar ratio of ammonia to benzaldehyde is controlled to be 0.5:1, then the methanol solution and hydrogen gas are mixed in an inlet micro-sieve-pore micro-mixer 2, the formed gas-liquid mixture passes through a micro packed bed reactor filled with a palladium carbon catalyst, the reaction temperature is controlled to be 100 ℃, the pressure is 10.0MPa, the residence time is controlled to be 2min, gas-liquid phase separation is carried out at the outlet of the micro packed bed, the obtained methanol solution is analyzed, the conversion rate of the reaction is 100%, and the yield of dibenzylamine is.
Example 3:
according to the method, an experiment is carried out, a propanol solution of p-tert-butyl benzaldehyde is prepared, the concentration is 20 wt%, a phase transfer catalyst of benzyltriethylammonium chloride is added, the addition amount is 0.5% of the concentration of a substrate to be hydrogenated, the benzyltriethylammonium chloride and ammonia water are mixed in an inlet T-shaped micro mixer 1, the molar ratio of ammonia to benzaldehyde is controlled to be 5:1, then the benzyltriethylammonium chloride and hydrogen are mixed in an inlet membrane dispersion micro mixer 2, the formed gas-liquid mixture passes through a micro packed bed reactor filled with a ruthenium alumina catalyst, the reaction temperature is controlled to be 80 ℃, the pressure is 4.0MPa, the residence time is controlled to be 3min, gas-liquid phase separation is carried out at the outlet of the micro packed bed, the obtained propanol solution is analyzed, the conversion rate of the reaction is 100%, and the.
Example 4:
according to the method, an experiment is carried out, a methanol solution of benzaldehyde is prepared, the concentration of the methanol solution is 40 wt%, the methanol solution and ammonia gas are mixed in an inlet membrane dispersion micro-mixer 1, the molar ratio of ammonia to benzaldehyde is controlled to be 8:1, then the methanol solution and hydrogen gas are mixed in an inlet T-shaped micro-mixer 2, the formed gas-liquid mixture passes through a micro packed bed reactor filled with a nickel-alumina catalyst, the reaction temperature is controlled to be 120 ℃, the pressure is controlled to be 5.0MPa, the residence time is controlled to be 30min, gas-liquid phase separation is carried out at the outlet of the micro packed bed, the obtained methanol solution is analyzed, the conversion rate of the reaction is 100%, and the yield of benzylamine is.
Example 5:
according to the method, an ethanol solution of benzaldehyde is prepared, the concentration of the ethanol solution is 15 wt%, a phase transfer catalyst tetrabutylammonium bromide is added, the addition amount of the tetrabutylammonium bromide is 0.2% of the concentration of a substrate to be hydrogenated, the tetrabutylammonium bromide and ammonia water are mixed in an inlet membrane dispersion micro-mixer 1, the molar ratio of the ammonia to the benzaldehyde is controlled to be 1:1, then the tetrabutylammonium bromide and hydrogen are mixed in an inlet membrane dispersion micro-mixer 2, the formed gas-liquid mixture passes through a micro packed bed reactor filled with palladium/alumina, the reaction temperature is controlled to be 80 ℃, the pressure is controlled to be 5.0MPa, the retention time is controlled to be 6min, gas-liquid phase separation is carried out at the outlet of the micro packed bed, the obtained ethanol solution is analyzed, the conversion rate of the reaction is 100%, and.
Industrial applicability
The device and the method of the invention utilize the high-efficiency mixing and excellent mass transfer and heat transfer performance of the microreactor, strengthen the capacity of interphase mass transfer and heat transfer in the reaction process, obviously reduce the volume of the reactor, improve the reaction yield and improve the production efficiency and safety.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A method for continuously synthesizing benzylamine substances through heterogeneous hydrogenation in a microreactor, which uses an apparatus for continuously synthesizing benzylamine substances through heterogeneous hydrogenation in the microreactor, and the apparatus comprises: the device comprises an inlet micro mixer (1), an inlet micro mixer (2), a micro packed bed reactor (3) and an outlet phase splitting tank (4), wherein the inlet micro mixer (1) is used for mixing a substrate to be hydrogenated with an ammonia source to form a mixed solution; the inlet micro mixer (2) is used for mixing the first mixed liquid with hydrogen to form gas-liquid mixed fluid; the micro packed bed reactor (3) is filled with a solid catalyst and is used for carrying out heterogeneous hydrogenation reduction reaction; the outlet phase separation tank (4) is used for separating gas and liquid of the reacted liquid, wherein the micro mixer comprises a membrane dispersion reactor, a micro-sieve reactor and a T-shaped reactor or other micro reactors capable of realizing the mixing of the system, and the solid particle catalyst is palladium carbon catalyst, palladium/alumina, platinum carbon, ruthenium carbon catalyst, ruthenium/alumina, nickel/alumina or Raney nickel catalyst;
the method comprises the following steps:
(1) preparing a solution of a substrate to be hydrogenated, mixing the substrate to be hydrogenated with an ammonia source in an inlet micro mixer (1), and mixing the formed mixed solution with hydrogen in an inlet micro mixer (2) to form a gas-liquid mixed fluid;
(2) enabling the gas-liquid mixed fluid obtained in the step (1) to flow through a micro packed bed reactor (3) filled with a solid particle catalyst to carry out heterogeneous hydrogenation reduction reaction;
(3) and (3) in an outlet phase-splitting tank (4), carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), returning the separated hydrogen to the micro mixer (2) in the step (1) for recycling, and separating and purifying the separated solution to obtain a benzylamine substance, wherein the mass concentration of the substrate to be hydrogenated in the organic solvent is 5-40 wt%, and the substrate to be hydrogenated is selected from benzaldehyde and tert-butyl benzaldehyde.
2. The method of claim 1, wherein the solvent for dissolving the hydrogenation substrate is one or more of methanol, ethanol, propanol and ethyl acetate.
3. The method according to any one of claims 1-2, wherein the ammonia source is ammonia gas or ammonia water, wherein the mass concentration of the ammonia water is 25-40 wt%.
4. The process according to any one of claims 1-2, wherein the molar ratio of the ammonia source to the substrate to be hydrogenated is from 0.5 to 15: 1.
5. The method according to any one of claims 1 to 2, wherein one or more of tetraethylammonium chloride, tetrabutylammonium hydroxide, benzyltriethylammonium chloride and tetrabutylammonium bromide are added to the substrate solution to be hydrogenated as a phase transfer catalyst in an amount of 0.2 to 0.5 wt% of the substrate concentration to be hydrogenated.
6. The process according to any one of claims 1-2, wherein the reaction temperature of the micro packed bed reactor (3) is between 30 ℃ and 150 ℃ and the pressure is between 0.4 and 10 MPa; the residence time of the gas-liquid mixture in the micro packed bed reactor (3) is 0.5-30 min.
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| CN113429295B (en) * | 2021-07-12 | 2022-12-20 | 浙江迪邦化工有限公司 | Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor |
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